CN104549444B - The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application - Google Patents
The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application Download PDFInfo
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- CN104549444B CN104549444B CN201310512756.XA CN201310512756A CN104549444B CN 104549444 B CN104549444 B CN 104549444B CN 201310512756 A CN201310512756 A CN 201310512756A CN 104549444 B CN104549444 B CN 104549444B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- -1 template Chemical compound 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000005995 Aluminium silicate Substances 0.000 claims 1
- 235000012211 aluminium silicate Nutrition 0.000 claims 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005899 aromatization reaction Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000011701 zinc Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the method for a kind of catalyst of oxygenatedchemicals aromatic hydrocarbons and oxygenatedchemicals aromatic hydrocarbons, mainly solves existing catalyst when for oxygenatedchemicals aromatisation, the selectively low technical problems with stability difference of BTX be present.The present invention is raw material by using oxygenatedchemicals, is 350 ~ 550 DEG C in temperature, pressure is 0.1 ~ 2MPa, and raw material weight air speed is 0.1 ~ 6h‑1Under conditions of, raw material is in contact with catalyst, obtains the effluent containing aromatic hydrocarbons, and used catalyst is selected from P by weight percentage, comprising 0.5 ~ 8%2O5, 0 ~ 5% be selected from La2O3Or Fe2O3At least one of, 30 ~ 80% selected from directly synthesize contain ZnO or Ga2O3The molecular sieves of ZSM 5,15 ~ 65% be selected from the technical scheme selected from least one of aluminum oxide or silica, preferably solve the problem, in the industrial production available for oxygenatedchemicals aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of oxygenatedchemicals arenes catalytic agent and the method for oxygenatedchemicals aromatic hydrocarbons.
Background technology
Aromatic hydrocarbons (wherein benzene, toluene and dimethylbenzene is referred to as B, T and X, and three is referred to as BTX) is important substantially organic
Industrial chemicals.Aromatic hydrocarbons is mainly derived from catalytic reforming and steam cracking by-product drippolene (close to 90%)-petroleum path, comes
What it is from coal route is only 10% or so.From the point of view of energy source distribution, China's oil starvation, lack gas still rich coal, external crude oil dependency degree
50% is alreadyd exceed, this has threatened national energy security.And petroleum resources are increasingly exhausted, the long-term high-order shake of oil price
Swing, this causes the derived energy chemical based on petroleum path to face unprecedented severe challenge, thus exploitation replaces petroleum path
The new technology for producing aromatic hydrocarbons is imperative.The coal methanol in China just gradually moves towards maximization, and yield is constantly soaring, it is contemplated that 2015
Year, China's methanol ability was total up to 50,000,000 tons/year, and production capacity will substantially exceed actual demand.From resourceful coal-based methanol
Direct preparing aromatic hydrocarbon by converting, for alleviate aromatic hydrocarbons shortage, improve Downstream Products of Methanol added value, extend coal chemical industry and natural
Gas chemical industrial chain, all with strategic meaning.
Chinese patent CN1880288A etc. is reported using methanol as raw material, and catalyst is load Ga and the ZSM-5 of La components
Molecular sieve is catalyst, and in pressure 0.1-3.5MPA, 380-500 DEG C of reaction temperature, methanol volume space velocity is 0.1-10.0h-1, N2
Air speed is:120-800h-1Reaction condition under, arene content in liquid-phase product is up to 70%.
Chinese patent CN101204969 reports a kind of device of recirculating fluidized bed methanol aromatic hydrocarbons, catalyst Zn,
The siliceous of the metal-modifieds such as Ag, Mo, Pt, Au, aluminium and phosphorus component molecular sieve catalyst, the yield of aromatic hydrocarbons select more than 70%, BTX
The low yield for being more than 55%, BTX of selecting property is only 40% or so.
Chinese patent reports a kind of technique and catalyst method for improving aromatization of methanol catalyst choice, the patent
It is disclosed in 0.1~0.5Mpa of reaction pressure, 350~500 DEG C of reaction temperature, 0.1~10h of raw material volume air speed-1And N2 body
Product air speed is 120~800h-1Under conditions of, the selectivity of aromatic hydrocarbons is 55~70%.
Although prior art report, the aromatics yield of oxygenatedchemicals aromatisation is higher, exist BTX selectivity with stably
Property difference technical problem.In the composition of aromatic hydrocarbons, light aromatic hydrocarbons --- BTX is that have highest economic value and the most wide aromatic hydrocarbons of purposes
Product.Wherein heavy arene, such as trimethylbenzene, durene, component is numerous and jumbled, and purposes is limited and demand is low, typically needs further
Light aromatic hydrocarbons are converted into, so add the cost of light aromatic hydrocarbons production.In oxygenatedchemicals aromatization process, catalyst have compared with
High BTX selectivity is advantageous to improve the economy of the process, and significant economic value is created for enterprise.Oxygenatedchemicals virtue
Structureization is reacted, the easy carbon deposit of catalyst, the bad technical problem of catalyst existence and stability.
The content of the invention
When one of technical problems to be solved by the invention are that existing catalyst is applied to oxygenatedchemicals aromatization process,
The problem of BTX selectively low and activity stability difference be present, propose a kind of new oxygenatedchemicals aromatized catalyst, the catalysis
Agent is applied to oxygenatedchemicals aromatic hydrocarbons process, has the advantages of BTX is selectively high and activity stabilized good.
The two of the technical problems to be solved by the invention are to provide a kind of catalyst for preparing and solving one of technical problem
Method.
The three of the technical problems to be solved by the invention be to provide it is a kind of using the catalyst for solving one of technical problem by
The method that oxygenatedchemicals prepares aromatic hydrocarbons, this method have the advantages of arenes selectivity is high, high income.
To solve one of above-mentioned technical problem, the technical solution adopted in the present invention is as follows：A kind of oxygenatedchemicals system virtue
The catalyst of hydrocarbon, in terms of catalyst weight percent, include following components：
A) 0.5~8% it is selected from P2O5；
B) 0~5% it is selected from La2O3Or Fe2O3At least one of；
C) 30~80% contain ZnO or Ga selected from what is directly synthesized2O3ZSM-5 molecular sieve；
D) 15~65% at least one of aluminum oxide or silica are selected from.
In above-mentioned technical proposal, containing ZnO or Ga2O3ZSM-5 molecular sieve in, ZnO or Ga2O3With SiO in molecular sieve2Rub
You are than being 0.5~10:100；Selected from La2O3Or Fe2O3At least one of oxide the preferable scope of dosage for 0.5~
2.5%；Containing ZnO or Ga2O3ZSM-5 molecular sieve SiO2With Al2O3Mol ratio is 20~300；Containing ZnO or Ga2O3ZSM-5
The SiO of molecular sieve2With Al2O3The preferable scope of mol ratio is 20~150；
To solve the two of above-mentioned technical problem, the technical solution adopted in the present invention is as follows：One kind contains ZnO or Ga2O3's
The preparation method of ZSM-5 or ZSM-11 molecular sieves, including following steps：
A) with molar ratio computing, according to (0.8~13) Ga2O3Or ZnO：(0.33~4) Al2O3：100SiO2：(0~40)
NaOH：(0~100) template：(1000~5000) H2O ratio, by Zn salt or Ga salt and Ludox, aluminium salt, template, hydrogen
Sodium oxide molybdena, water, it is well mixed；
B) at 120~180 DEG C, 12~120h of crystallization；
C) crystallization product is scrubbed, dries, and 2~12h removed template methods are calcined at 500~600 DEG C, obtain sodium form molecule
Sieve.
In above-mentioned technical proposal, template used dose is ethylenediamine, triethylamine, n-butylamine, 4-propyl bromide, tetrapropyl hydrogen
At least one of amine-oxides and hexamethylene diamine.
Preferred technical scheme, containing ZnO or Ga2O3Direct synthesis ZSM-5 molecular sieve preparation procedure it is as follows：With
Molar ratio computing, according to (1~5) Ga2O3Or ZnO：(0.5~3) Al2O3：100SiO2：(1~20) NaOH：(10~60) template：
(1000~3000) H2O, after Zn salt or Ga salt are well mixed with Ludox, aluminium salt, template, sodium hydroxide, water, it is transferred to close
The crystallizing kettle closed at 120~180 DEG C after 14~100h of crystallization, wherein template can be ethylenediamine, triethylamine, n-butylamine,
At least one of 4-propyl bromide, TPAOH and hexamethylene diamine.After crystallization terminates, crystallization product is scrubbed,
Dry, 2~10h removed template methods are calcined at 500~600 DEG C and obtains sodium form and contains ZnO or Ga2O3Molecular sieve.Synthesis journey above
In sequence, the ZnO or Ga of synthesis2O3The preferable scope of ZSM-5 molecular sieve crystallization temperature be 140~180 DEG C, crystallization time is preferred
20~70h of scope.
To solve the three of above-mentioned technical problem, the technical solution adopted in the present invention is as follows, uses oxygenatedchemicals as original
Material, it is 350~550 DEG C in temperature, pressure is 0.01~2MPa, and raw material weight air speed is 0.1~6h-1Under conditions of, raw material with
Catalyst is in contact, and obtains the effluent containing aromatic hydrocarbons.
In above-mentioned technical proposal, the preferable scope of reaction temperature be 410~480 DEG C, the preferable scope of pressure be 0.1~
1MPa, the preferable scope of raw material weight air speed are 0.2~2.0h-1。
The preparation procedure of catalyst is as follows：At 60~90 DEG C, the sodium form sodium form of synthesis is contained into ZnO or Ga2O3Molecular sieve
Swapped 2 hours, be repeated 3 times with 1M nitric acid ammonia solution, solid-to-liquid ratio 1:5~20, then through drying, at 500~600 DEG C
Roasting obtains hydrogen type molecular sieve.The desired amount of hydrogen type molecular sieve is weighed, with aluminum oxide or silica binder, pore creating material and dilute
Nitric acid is wet to be pinched, is molded.Aluminum oxide comes from boehmite, and silica comes from Ludox.Pore creating material may be selected from sesbania powder, polyethylene
At least one of alcohol, cellulose, dosage are the 1~6% of inoganic solids weight.Carrier after shaping is done at 100~120 DEG C
Dry 6~24h, 1~12h is calcined at 500~650 DEG C.The desired amount of roasting carrier is taken, is contained using incipient impregnation and is selected from B) with
C the aqueous solution of component in), it is aged at room temperature 6~24 hours, 6~24h is then dried at 100~120 DEG C, 500~650
1~12h is calcined at DEG C and obtains catalyst.
Oxygenatedchemicals aromatized catalyst, typically by dehydrogenation component --- Ga or Zn, acidic components molecular sieve are formed.
Existing oxygenatedchemicals aromatized catalyst, dehydrogenation component is mostly loaded using infusion process or ion-exchange --- Ga or
Dehydrogenation component be present and the problem of not uniform enough be distributed on carrier in Zn, this method.By directly synthesizing, Zn or Ga elements can enter
The skeleton for entering framework of molecular sieve or molecular sieve exchanges position so that Zn or Ga components can be supported on ZSM-5 molecular sieve with high dispersive
Skeleton or duct in, more preferable modification can be played to the skeleton of molecular sieve, promote oxygenatedchemicals aromatization,
Inhibit the repeatedly side reaction such as alkylation, the selectivity and stability of the catalyst of raising.
The present invention contains ZnO or Ga using what is directly synthesized2O3ZSM-5 molecular sieve prepare oxygenatedchemicals for active component
Aromatized catalyst, using 100% oxygenatedchemicals as raw material, at 410 DEG C, WHSV=1.0h-1And the reaction condition of normal pressure
Under, the yield of aromatic hydrocarbons, up to 68~83%, higher than existing catalyst 8~13%, reacts 24 up to 45~64%, BTX selectivity
After hour, aromatics yield retention rate up to 75~83%, the BTX yield retention rates of the catalyst prepared than existing method are high by 8~
14%, achieve preferable technique effect.
Below by specific embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
According to 13.0ZnO：4Al2O3：100SiO2：24NaOH：30 ethylenediamines：5000H2O mol ratio, weigh 67.5 grams
Aluminum nitrate, 225 grams of Ludox (40%SiO2), 14.4 grams of sodium hydroxides, 27 grams of ethylenediamines, 1215 grams of water are mixed
After rubber alloy body, colloid mixture is transferred in closed crystallizing kettle at 180 DEG C after crystallization 12h, it is scrubbed, dry, at 600 DEG C
4 hours removed template methods of roasting obtain the ZnZSM-5 of sodium form.At 90 DEG C, the ZnZSM-5 molecular sieve 5w% concentration that will obtain
Nitric acid ammonia spirit exchange 2 hours, be repeated 3 times, solid-liquid weight ratio be 1:5, then through drying, it is calcined 4 hours at 600 DEG C
Obtain Hydrogen ZnZSM-5 molecular sieves.The composition of Zeolite synthesis precursor in embodiment 1-8 is listed in table 1 with crystallization condition.
Weigh 30 grams of Hydrogen ZnZSM-5 molecular sieves, 94.4 grams of boehmite (70%Al2O3), 3.3 grams of sesbania powders, use
The dust technology that weight content is 3.0% wet pinched, is molded.Carrier after shaping is dried 6 hours at 120 DEG C, is calcined at 600 DEG C
4 hours.30 grams of roasting carriers are taken, 20.9 grams of aqueous solution containing 0.76 gram of ferric nitrate are impregnated using equi-volume process, are aged at room temperature
12 hours, 6h is then dried at 120 DEG C, 6h is calcined at 550 DEG C and obtains catalyst a, catalyst composition is listed in table 2.
【Embodiment 2~8】
The raw material proportioning provided according to table 1, using step same as Example 1, prepare Hydrogen ZnZSM-5 or
GaZSM-5 molecular sieves.
The composition provided according to table 1, catalyst b~h, the composition of catalyst are obtained using step same as Example 1
2 can be shown in Table.
【Comparative example 1】
Using the molecular sieve of silica alumina ratio in the same manner as in Example 1, using similar program load zinc, phosphorus component.
【Comparative example 2】
Using the molecular sieve of silica alumina ratio in the same manner as in Example 4, using similar program load zinc and lanthanum component.
【Embodiment 9~12】
Embodiment 9~12 is using catalyst e, changes the differential responses result that process conditions obtain, and appraisal result is shown in Table
3。
Table 1
Table 2
The SiO in molecular sieve in table 22/Al2O3, ZnO or Ga2O3/SiO2The ratio between be mol ratio.
Table 3
Claims (8)
1. a kind of catalyst of oxygenatedchemicals aromatic hydrocarbons, in terms of catalyst weight percent, includes following components：
A) 0.5~8% it is selected from P2O5；
B) 0~5% it is selected from La2O3Or Fe2O3At least one of；
C) 30~80% contain ZnO or Ga selected from what is directly synthesized2O3At least one of ZSM-5 molecular sieve；
D) 15~65% selected from least one of aluminum oxide, silica or kaolin；
Wherein, containing ZnO or Ga2O3ZSM-5 in ZnO or Ga2O3With the SiO in molecular sieve2Mol ratio be 0.5~10:
100；
Containing ZnO or Ga2O3ZSM-5 molecular sieve preparation method, including following steps：
A) with molar ratio computing, according to (1~5) Ga2O3Or ZnO：(0.5~3) Al2O3：100SiO2：(1~20) NaOH：(10~
60) template：(1000~3000) H2O ratio, by Zn salt or Ga salt and Ludox, aluminium salt, template, sodium hydroxide, water,
It is well mixed；
B) at 120~180 DEG C, 12~120h of crystallization；
C) crystallization product is scrubbed, dries, and 2~12h removed template methods are calcined at 500~600 DEG C, obtain sodium form molecular sieve；
Template used dose is in ethylenediamine, triethylamine, n-butylamine, 4-propyl bromide, TPAOH and hexamethylene diamine
At least one.
2. the catalyst of oxygenatedchemicals aromatic hydrocarbons according to claim 1, it is characterised in that with catalyst weight percentage
Than meter, La is selected from containing 0.5~2.5%2O3Or Fe2O3At least one of.
3. the catalyst of oxygenatedchemicals aromatic hydrocarbons according to claim 1, it is characterised in that directly synthesize containing ZnO or
Ga2O3ZSM-5 molecular sieve SiO2With Al2O3Mol ratio be 20~300.
4. the catalyst of oxygenatedchemicals aromatic hydrocarbons according to claim 1, it is characterised in that directly synthesize containing ZnO or
Ga2O3ZSM-5 molecular sieve SiO2With Al2O3Mol ratio be preferably 20~150.
5. the catalyst of oxygenatedchemicals aromatic hydrocarbons according to claim 1, wherein the ZnO or Ga that synthesize2O3ZSM-5
Crystallization of Zeolite temperature is 140~180 DEG C, and crystallization time is 20~70h.
It is 350~550 DEG C in temperature 6. a kind of method for producing aromatic hydrocarbons, use oxygenatedchemicals as raw material, pressure is 0.01~
2MPa, raw material weight air speed are 0.2~6h-1Under conditions of, raw material is in contact with the catalyst described in claim 1, obtains
Effluent containing aromatic hydrocarbons.
7. the method for production aromatic hydrocarbons according to claim 6, it is characterised in that oxygenatedchemicals is methanol, ethanol or diformazan
At least one of ether.
8. the method for production aromatic hydrocarbons according to claim 6, it is characterised in that temperature is 410~480 DEG C, pressure 0.1~
1MPa, 0.2~2.0h of raw material weight air speed-1。
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| CN106607083B (en) * | 2015-10-21 | 2019-05-14 | 中国石油化工股份有限公司 | The catalyst and its application method of synthesis gas aromatic hydrocarbons |
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